Neste trabalho foram desenvolvidos métodos eletroanalíticos (redissolução potenciométrica e voltamétrica) para a determinação de metais (mercúrio, cobre, chumbo e zinco) em petróleo, óleo diesel, óleo lubrificante e álcool combustível. Para analisar álcool, foi também desenvolvido um método por eletroforese capilar, que possibilita a determinação de cátions (sódio, potássio e cálcio) e ânions (cloreto, sulfato e nitrato). Procedimentos envolvendo a utilização de fornos de microondas (focalizadas - que opera a pressão atmosférica - e com cavidade, que promove a digestão em frascos pressurizados) para a decomposição de petróleo, óleo diesel e óleo lubrificante são descritos. As determinações de cobre e mercúrio por redissolução potenciométrica apresentaram melhores limites de detecção do que a voltametria de redissolução de onda quadrada nas amostras digeridas, utilizando eletrodos de ouro confeccionados a partir de CDs graváveis (Cdtrodos), como eletrodo de trabalho. Para a determinação de chumbo e zinco nas mesmas amostras digeridas, os melhores resultados foram obtidos com eletrodos de filme de mercúrio e utilizando a voltametria de redissolução potenciométrica. Perdas de mercúrio por volatilização foram verificadas quando as amostras foram digeridas em fornos de microondas focalizadas. Para os demais metais, a utilização deste forno foi vantajosa por proporcionar melhores limites de detecção devido à utilização de maiores massas de amostra no processo de digestão. A utilização de um banho ultrassônico de bancada para promover a extração de cobre e chumbo de óleos lubrificantes na presença da mistura 1:1 (v/v) de HClconc. e H2O2 (30% m/v) mostrou-se eficiente. Trinta minutos de exposição à energia ultrassônica foram necessários para a extração quantitativa de ambos os metais. Nas soluções extratoras, o teor dos metais foi determinado por voltametria de redissolução anódica, usando CDtrodos. Os limites de detecção do método para a determinação de cobre e chumbo foram, respectivamente, de 23 e 67 ng g-1 de óleo, aplicando 120 s de tempo de deposição. A voltametria de redissolução anódica em eletrodo de ouro possibilitou a determinação de cobre e chumbo em álcool combustível, sem qualquer tratamento prévio das amostras. Limites de detecção de 120 e 235 ng L-1 para cobre e chumbo, respectivamente, foram obtidos aplicando 15 min de tempo de deposição. Alternativamente, a evaporação do etanol seguido da redissolução em água desionizada permitiu a determinação dos metais por análise de redissolução. Todos os resultados obtidos utilizando diferentes metodologias de decomposição de amostras foram comparados com os resultados obtidos por análises por espectrometria de absorção atômica com forno de grafite. O método envolvendo a evaporação prévia, seguida da redissolução dos íons em meio aquoso também se mostrou muito favorável para realizar a determinação de cátions e ânions por eletroforese capilar em amostras de etanol hidratado combustível. Os íons Na+, K+ e Ca2+, Cl-, NO3- e SO42- foram encontrados nas amostras analisadas. Os limites de detecção destes íons se encontram na faixa de 0,06 e 0,18 mg L-1. / In this work eletroanalytical methodologies (potentiometric stripping analysis and anodic stripping voltammetry) for the determination of metals (mercury, copper, lead, and zinc) in crude oil, lubricating oil, diesel fuel, and ethanol fuel are proposed. A capillary electrophoresis method for ethanol fuel was developed to determine cations (sodium, potassium, and calcium) and anions (chloride, sulphate, and nitrate). Microwave digestion methods using different ovens (a focused microwave oven – operating at atmospheric pressure, and a cavity microwave oven, which employs pressurized vessels) for crude oil, lubricating oil, and diesel fuel are described. The determination of copper and mercury by potentiometric stripping analysis presents better detection limits than stripping voltammetric determinations for the digested sample analysis. Loss of mercury by volatilization was verified when samples were digested in the focused microwave oven. Otherwise, this oven presented some advantages for the other metals, as the improved detection limits due to the employment of higher sample mass for the digestion process. The use of a ultrasonic bath to promote the extraction of copper and lead from lubricating oils in the presence of 1:1 (v/v) HClconc and H2O2 (30% m/v) was efficient. Thirty minutes of ultrasonic exposure were necessary for quantitative exctraction of copper and lead. Anodic stripping voltammetry using gold CDtrodes was applied for metal determination in the extracted solutions. The detection limits of the proposed method for copper and lead were 23 and 67 ng g-1, respectively, under application of 120 seconds as deposition time. Anodic stripping voltammetry at a gold electrode was used for the determination of copper and lead in ethanol fuel, without any prior sample treatment. Detection limits of 120 and 235 ng L-1 for copper and lead, respectively, were attained applying 900 s as deposition time. Alternatively, the ethanol evaporation followed by re-suspension in deionised water allowed the metals determination by stripping analysis. All results obtained for sample decomposition methods were compared with the ones obtained by electrothermal atomic absorption spectrometric determinations. The method, which employs prior ethanol evaporation followed by re-suspension in deionised water, was applied for the determination of cations and anions by capillary electrophoresis in the hydrated ethanol fuel (automotive fuel). Na+, K+, Ca2+, Cl-, NO3-, and SO42- ions were found in the analyzed samples. The detection limits for these ions were situated between 0.06 and 0.18 mg L-1.

[pt] O transporte eletrocinético de gasolina e óleo através de um solo residual gnáissico é focado na utilização da eletrocinese como uma técnica de remediação para solos finos. Baseia-se na aplicação de uma diferença de potencial através de uma massa de solo, com a conseqüente produção de um fluxo eletrocinético, o qual envolve mecanismos como eletroosmose -fluxo de água- e migração de íons.Na primeira etapa, amostras de solo foram contaminadas com gasolina e com óleo cru. Os ensaios mostraram que a presença desses compostos não variou o comportamento dos parâmetros eletroosmóticos, assim como o pH e a condutividade elétrica dos eletrólitos e do próprio solo. Em dois dos ensaios realizados com óleo, observou-se um notório transporte em direção ao anodo devido à eletroosmose. Já com a gasolina os resultados das determinações analíticas sugeriram o transporte da mesma, embora que em uma escala reduzida. Na segunda etapa analisou-se a remediação dos metais e do óleo presentes em uma borra de petróleo da Bacia de Campos, para a utilização desta como material geotécnico. Nenhum teor significativo de metal foi encontrado na borra antes do ensaio, em contrapartida, observou-se contaminação de zinco pela corrosão dos eletrodos de latão utilizados. E quanto ao óleo, notou-se um transporte considerável devido à eletroosmose. / [en] This study assesses the use of electrokinetics as an innovative technique for remediation of fine-grained soils. It relies on the application of an electrical potential through a soil mass, producing a series of coupled flows, including fluid flow -electroosmosis- and migration of ions. The first stage of the experimental program encompassed a series of tests with samples of residual soil contaminated with gasoline and crude oil. The results showed that the presence of these compounds did not affect the electroosmotic behavior, and there was observed no changes on the pH and electric conductivity of neither the electrolytes solution nor the soil itself.When oil contaminated samples are of concern, it was noticed a clear electroosmotic flow towards the anode. This pattern was also observed, but at a reduced level, on the tests on the gasoline contaminated samples.The second stage of the experimental program consisted on a series of tests with oil ground from Campos Basin aiming on dewatering and de-oiling. The results were satisfying, in all sample there was a noticeable reduction on the water and oil contents. Tests results also showed a zinc contamination on the sample caused by electrolysis on the brass electrodes.

Ce travail présente une étude de la dynamique interfaciale de gouttes oscillantes dans une plage étendue de fréquences, en particulier dans le domaine des hautes fréquences. Nous avons développé une méthode de caractérisation de la dynamique des oscillations de gouttes, en présence d’un forçage externe imposé, sous la forme de variations de volume périodiques de faible amplitude sur une goutte attachée à l’extrémité d’un capillaire. Cette méthode permet d’identifier les modes d’oscillation des gouttes et d’en mesurer les fréquences et les taux d’amortissement. Cette méthode a été appliquée à différents systèmes liquide-liquide, en l’absence ou en présence de surfactants. Dans ce dernier cas, elle permet d’évaluer l’effet du comportement viscoélastique des interfaces sur la dynamique des oscillations. Ainsi 3 types d’interfaces ont été identifiés. Pour les interfaces de premier type (heptane/eau sans ajout de surfactant), chaque mode propre est modélisé par un oscillateur linéaire peu amorti. Les fréquences propres et les taux d’amortissement sont bien prédits par la théorie linéaire. Les interfaces de types 2 et 3 sont obtenues en ajoutant du pétrole brut à la phase dispersée. Les surfactants naturellement présents dans le pétrole (asphaltènes, résines) s’adsorbent à l’interface et lui confèrent des propriétés viscoélastiques. Pour les interfaces jeunes (type 2, moins de 20 minutes de vieillissement), les fréquences propres mesurées restent bien prédites par la théorie, qui considère des interfaces non contaminées, tandis que les taux d’amortissement sont de loin supérieurs aux valeurs théoriques. D’autre part, les interfaces vieillies (type 3) présentent des modes propres différents avec des fréquences de résonance supérieures à celles des interfaces jeunes. Dans ce cas, la dynamique de l’interface à haute fréquence est régie par l’élasticité du réseau formé par les espèces amphiphiles du pétrole brut. Les oscillations libres d’une goutte en ascension dans une phase externe stagnante, pour un système liquide-liquide sans ajout de surfactants, ont été étudiées. Les valeurs mesurées de la fréquence d’oscillation des 4 premiers modes sont en adéquation avec la théorie linéaire. Cependant les valeurs mesurées du taux d’amortissement sont très élevées par rapport aux valeurs théoriques, pour une interface non contaminée. En effet, des espèces résiduelles adsorbées à l’interface provoquent l’apparition d’un gradient de tension interfaciale par effet Marangoni et par suite une production de vorticité plus intense dans les couches-limites, ce qui conduit à l’augmentation de l’amortissement des oscillations. / We present an experimental study of oscillating drop interfacial dynamics at a wide frequency range, especially at high frequency. A characterization method of drops oscillation dynamics has been developed. The oscillations are generated by imposing low amplitude periodic variation of volume to a drop which is attached to a capillary tip. The present method is based on the identification of the drop eigenmodes and the determination of their frequencies and damping rates. It has been applied to characterize several liquid-liquid systems. Three types of interface have been identified. For interfaces of type 1 (heptane/water without added surfactant), each eigenmode is modelled by a weakly damped linear oscillator. Eigenfrequencies and damping rates are well predicted by the linear theory. Interfaces of Types 2 and 3 are obtained by adding crude oil to the disperse phase. Oil native surfactants (asphaltenes, resins) adsorb on the drop interface and provide the latter with viscoelastic behaviour. For young interfaces (type 2 with aging time below 20 minutes), eigenfrequencies remain well predicted by the theory, which deals with non contaminated interfaces, whereas the measured damping rates are significantly higher than the theoretical values. On the other hand, aged interfaces (type 3) exhibit different eigenmodes, of which eigenfrequencies are much higher than the resonance frequencies measured for the young interfaces. At high frequency, the dynamics of aged interfaces are governed by the elasticity of the network constituted by the crude oil amphiphilic species, while the dynamics of young interfaces are governed by interfacial tension. Freely decaying oscillations of a rising drop in a liquid at rest without added surfactant were also considered. Measured frequencies for the first four eigenmodes are in good agreement with the linear theory. However, measured damping rates are much higher than the theoretical rates for non contaminated interfaces. In fact, residual adsorbed species at the heptane/water interface induce Marangoni effects and thus gradients of interfacial tension. Therefore, vorticity production within the boundary layers is enhanced, which explains the observed increase of the oscillation damping rates.

The thesis is focused on the changes in the terms of trade in Czech international trade in the term of from 2005 to 2015, as the period after the Czech Republic joined the European Union. The terms of trade are an important indicator of the benefits and loses of international trade. The main aim is to analyze the changes of terms of trade, the causes of their changes, and the impact on the real economy. The direction of the overall terms of trade index was highly unsettled, and did not actually generated additional gains in the economy not over the reporting period. The overall terms of trades were most influenced by the price development of two groups of the Standard International Trade Classification, Crude materials and lubricants, and machinery and transport equipment. The prices of Crude materials and lubricants are determined mainly by changes in the oil prices. These were very volatile in the reporting period, the especially the collapse of the prices in both 2009 and 2014-2015, had a significant impact on the import prices of the Czech economy. The thesis also analyzes the impact of exchange rate on the international trade prices, in the period since November 2013, i.e. after the Czech National Bank has committed to maintain the rate of Czech koruna against the Euro above the level of 27 CZK/EUR, which helped to protect the economy from deflations and enhance the economic growth. The effect of the weak crown, that favored the Czech exporters, however a faded over time.

Scope of work was technical-commercial analyze with the aim of finding out if the foundation of a specialized subsidiary company by maintenance department outsourcing would have a real and economical justness. The specialized subsidiary would receive right and know-how of patented modern technology the DS Jet mixers designated for crude oil tank mixing and cleaning. Outcome of the thesis is found break-even point when applies the plan in terms of organizational-economical matters and which action would be necessary taken. Theoretical part of work explains specific of enterprise in new sphere of business, new technologies and services trends in Europe. There are discussed typical Europe crude oil market issues, explained principals of market and product analyze, internal process optimization methods and outsourcing in this part. Financial and break-even point analyzes is defined. Practical and analytical part includes the DS Jet Mixers technology description, implementation of the system in the MERO ČR, a. s. and the technology SWOT analyzes inclusive of competition benchmark. With market research had been checked EU market opportunities and marked attractive markets. The way of subsidiary foundation is proposed. The Integral part of the analytical part creates intended the break-even point. In the summary is comprehensive analyzes outcomes and recommended solution in current statute. Furthermore is advised marginal number of orders since when outsource the activities with the DS Jet mixers into subsidiary company.

La présence d'hétéroatomes et métaux dans des fractions lourdes de pétrole brut peuvent entraîner la désactivation des catalyseurs d’hydrotraitement et d’hydrocraquage. Les composés contenant ces éléments sont connus pour être inclus dans des agrégats macromoléculaires d’asphaltènes, qui sont considérées comme les composants les plus problématiques des produits pétroliers. Ces travaux ont pour objectif d’apporter une meilleure compréhension de l’environnement chimique de ces espèces et des phénomènes d’agrégation pour optimiser les processus de raffinage. Des techniques de séparation comme la chromatographie de perméation de gel ou Gel Permeation Chromatography (GPC), Advanced Polymer chromatographie (APC) et la chromatographie sur couche mince d’haute performance ou High Performance Thin Layer Chromatography (HPTLC) ont été combinées avec des techniques d’analyse élémentaire comme la spectrométrie de masse à plasma à couplage inductif ou Inductively Coupled Plasma Mass Spectrometry (ICP-MS) et la spectrométrie de masse moléculaire d’haute résolution pour la caractérisation des fractions pétrolières lourdes. Les profils de distribution en taille d’espèces qui contiennent du vanadium, du nickel et du soufre, les hétéroatomes et métaux les plus abondants dans les produits pétroliers, ont été déterminés par GPC couplé à une détection élémentaire par ICP MS. Les paramètres ayant le plus d’impact sur la distribution en taille et l’évolution des agrégats dans les solutions de différentes coupes pétrolières ont été optimisés. Cela nous a permis de faire différentes comparaisons, entre de nombreuses charges et effluents de procédés, ainsi que d’autres séries d’échantillons ou de mélanges provenant d’unités-pilotes d’hydrotraitement. Les résultats obtenus ont pu être mis en regard de caractéristiques macroscopiques comme la viscosité. Le couplage du nouveau système APC avec l’ICP MS a été mis au point avec succès. Cette technique a permis de réaliser des cartographies d’échantillons pétroliers plus rapides qu’en GPC tout en consommant moins de solvant. Cependant, les différences des chromatogrammes APC obtenus par rapport aux profils GPC suggèrent des interactions indésirables avec la phase stationnaire, qui ont été l’objet d’une évaluation approfondie.Enfin, un dernier type de séparation a été évaluée. L’HPTLC, qui utilise des plaques à usage unique, peut être appliquée à la séparation de produits lourds par polarité, et ce sans étapes de déasphaltage préalable, contrairement aux colonnes de chromatographie liquide qui peuvent être détériorées à cause de l'adsorption irréversible et de la précipitation des asphaltènes. Différents types de plaques et éluants ont été testés afin de développer une méthode simple pour la séparation des fractions SAR (Saturés, Aromatiques et Résines) des échantillons de distillat sous vide ou Vacuum Gas Oil (VGO). Ce travail avait pour but des migrations en une seule étape et analyse UV qui pourrait être mis en œuvre pour l’analyse de routine dans les laboratoires de contrôle avec une adsorption irréversible réduite. Des résultats très prometteurs ont été obtenus avec l’utilisation de plaques de cellulose pour la séparation des familles de polarité différentes au sein des agrégats d’asphaltènes. Des tests sur l'analyse directe des plaques par Désorption-Ionisation par Électronébulisation (DESI) MS, l'analyse directe en temps réel ou Direct Analysis in Real Time (DART) MS et Ablation Laser (LA) ICP MS ont été effectués. / The presence of heteroatoms and metals in heavy fractions of crude oil can cause the deactivation of hydrotreatment and hydrocracking catalysts. Compounds containing these elements are known to be included in macromolecular asphaltene aggregates, which are considered the most problematic components of heavy oil. This thesis aimed for a better understanding of the chemical environment of these species and on the aggregation phenomenon to optimize refining processes. Separation techniques such as Gel Permeation Chromatography (GPC), Advanced Polymer Chromatography (APC) and High Performance Thin Layer Chromatography (HPTLC) were combined with elementary analysis techniques such as Inductively Coupled Plasma Mass Spectrometry (ICP MS) or high-resolution molecular mass spectrometry for the characterization of heavy fractions of crude oil. Here, the size profiles of species that contain vanadium, nickel and sulfur, the most abundant heteroatoms and metals present in petroleum products, were determined by GPC online with elemental detection by ICP MS. The parameters having the most significant impact on size distribution and the evolution over time of aggregates from solutions of different petroleum cuts were optimized. This allowed the comparison between various feeds and effluents and other series of samples and mixtures from pilot units of refining processes by GPC ICP MS. Results obtained could be related to macroscopic characteristics such as viscosity. Hyphenation of the new APC System to ICP MS has been successfully completed. It allowed the mapping of petroleum samples faster than GPC, therefore with less solvent consumption. However, the differences of the APC chromatograms obtained with respect to the GPC profiles suggested significant unwanted interactions of the highly polar compounds of the petroleum samples with the stationary phase, which have been thoroughly studied. Finally, another type of separation was evaluated. HPTLC, of single-use plates, can be applied to the analysis of heavy petroleum products by polarity without prior deasphalting steps while chromatography columns can be deteriorated because of the irreversible adsorption and asphaltene precipitation. To this end, various types of plates and eluents were tested to develop straightforward SAR (Saturates, Aromatics and Resins) separations of Vacuum Gas Oil (VGO) samples. This method, based on single-step migrations with reduced irreversible adsorption and UV monitoring, could be implemented for routine analysis in control laboratories. Very promising results were obtained by the use of cellulose plates for the separation of different families within asphaltene aggregates. Tests on Desorption ElectroSpray Ionization (DESI) MS, Direct Analysis in Real Time (DART) MS and Laser Ablation (LA) ICP MS analyses of the plates have been performed.

<p>Crude oil is a mixture of hydrocarbons so complex that it is predicted to comprise as many compounds as there are genes in the human genome. Developing methods to not only recover crude oil from the ground but also to convert crude oil into desirable products is challenging due to its complex nature. Thus, the petroleum industry relies heavily on analytical techniques to characterize the oil in reservoirs prior to enhanced oil recovery efforts and to evaluate the chemical compositions of their crude oil based products. Mass spectrometry (MS) is the only analytical technique that has the potential to provide elemental composition as well as structural information for the individual compounds that comprise petroleum samples. The continuous development of ionization techniques and mass analyzers, and other instrumentation advances, have primed mass spectrometry as the go-to analytical technique for providing solutions to problems faced by the petroleum industry. The research discussed in this dissertation can be divided into three parts: developing novel mass spectrometry-based methods to characterize mixtures of saturated hydrocarbons in petroleum products (Chapters 3 and 5), exploring the cause of fragmentation of saturated hydrocarbons upon atmospheric pressure chemical ionization to improve the analysis of samples containing these compounds (Chapter 4), and developing a better understanding of the chemical composition of crude oil that tightly binds to reservoir surfaces to improve chemically enhanced oil recovery (Chapter 6). </p>

[pt] Durante a gelificação por parafina, a rede de cristais de parafina modifica o comportamento do óleo cru. Ele muda de um material newtoniano de baixa viscosidade para um material com dependência temporal e de alta viscosidade com tensão limite do escoamento. Com isto, é totalmente desafiador descobrir a pressão minima de início do fluxo de petróleo gelificado com uma microestrutura tão complexa. Através da minha dissertação de mestrado, investigamos dois materiais viscoplásticos: um gel de cabelo com uma tixotropia desprezível e uma suspensão aquosa tixotrópica 2 por cento de laponita para imitar o início de fluxo de óleos gelificados. Para ambos os materiais, o gradiente de pressão axial mínimo necessário para o início do fluxo foi medido e os valores medidos estavam de acordo com a previsão do balanço de força convencional. Por outro lado, os casos da indústria exibiram que o balanço de força mencionado acima leva a uma superestimação da pressão mínima inicial. Em alguns estudos, uma explicação elicitada é o comportamento tixotrópico do petróleo gelificado, mas nossos resultados acima mencionados serviram para refutá-lo. Durante a primeira parte da minha tese de doutorado, buscamos verificar por laboratório porque o balanço de força não se aplica ao petróleo gelificado, em seguida, buscamos uma explicação fisicamente adequada para essa discrepância e também uma maneira confiável de prever a pressão mínima de início do escoamento. Nesta linha, mostramos o efeito do encolhimento do petróleo gelificado na discordância entre a tensão limite estática de escoamento e o gradiente de pressão mínimo necessário para iniciar o fluxo, através da reometria e do fluxo de fluido em um tubo. Em seguida, introduzimos uma equação de balanço de força modificada com o efeito de encolhimento incluído para obter o melhor estimação da pressão minima de início de escoamento. Outro elemento essencial sobre o início de escoamento de petróleo gelificado é descobrir uma estratégia confiável para modelar matematicamente a reologia do material. Na maioria dos modelos que visam prever o comportamento reológico de petróleo gelificado, as mudanças da microestrutura durante o fluxo são consideradas tixotrópicas; dependência temporal reversível. Porém, observamos em nossos experimentos com histórias de fluxo e térmicas bem controladas que o caráter irreversível da dependência temporal é bastante evidente. Assim, na segunda parte da tese, propomos um modelo baseado no desenvolvimentos anteriores de Souza Mendes e colaboradores que considera a dependência temporal irreversível observada experimentalmente para petróleo gelificado. A capacidade preditiva do modelo proposto é então avaliada através de comparações com dados experimentais. / [en] Throughout the wax gelation, the network of parafinn crystals modifies the behavior of waxy crude oil. It changes from a low viscosity Newtonian to a high viscosity time-dependent material with yield strength. Now, it is totally challenging to find out the restart pressure for gelled crude oil ow with such a complex microstructure. Through my Master s dissertation, we investigated two viscoplastic materials, namely a hair gel with a negligible thixotropy and a quite thixotropic 2 percent aqueous suspension of Laponite to mimic the startup flow of waxy crude oils. For both materials, the minimum axial pressure gradient required for the onset of flow was measured, and the measured values were in good agreement with the prediction of a conventional force balance. On the other hand, industry cases have exhibited that the just mentioned force balance leads to an overestimation of the minimum startup pressure gradient. In some studies, an elicited explanation is the thixotropic behavior of the gelled crude, but our results above-mentioned served to falsify it. Over the first part of my PhD thesis, we aimed to verify in the laboratory that why the force balance does not hold for gelled crude oil and then we sought a physically proper explanation for this discrepancy and also a reliable way to predict the minimum startup pressure gradient. Along these lines, we show the role of gelled crude oil s shrinkage in the discordance between static yield strength and required minimum pressure gradient to onset the flow, through rheometry and fluid flow in a tube. Then, we introduce a modified force balance equation with the role of shrinkage included to best estimate the minimum restart pressure gradient. Another essential element through the restart flow of gelled waxy crude is to find out a reliable strategy to mathematically model the material s rheology. In most models that aim at predicting the rheological behavior of gelled waxy crude oil, the microstructure changes during ow are assumed to be thixotropic (reversible time dependent). But, we observed in our experiments with well-controlled flow and thermal histories that the irreversible character of time dependence is quite evident. Thus, in the second part of thesis we propose a model based on previous developments by Souza Mendes and co-workers that accounts for the irreversible time dependence observed experimentally in a waxy crude oil. The predictive capability of the proposed model is then assessed via comparisons with experimental data.

The Deepwater Horizon oil spill released millions of barrels of oil into the Gulf of Mexico, impacting economically and ecologically important fishes. Polycyclic aromatic hydrocarbons (PAHs) present in the oil have been shown to cause developmental impairments in early life stage fishes, such as morphological and behavioral changes related to eye formation and visual processing following PAH exposure. Prior research reported reduced eye growth in open water, pelagic species, as well as reduced photoreceptor-specific transcription factors associated with eye development following exposure to crude oil. Though changes in transcriptomic-level pathways associated with vision and visual processing have been reported, it has yet to be determined how these changes relate to physiological or behavioral-level effects in fish. Therefore, the present studies evaluated the effect of weathered crude oil on eye development and visual function in mahi-mahi, red drum, sheepshead minnow, and zebrafish larvae. Fish were assessed through several visually-mediated behavioral assays, analyzed histologically and immunohistologically, along with subsequent transcriptomic analyses and associated gene expression changes. Larvae exposed to crude oil experienced significantly reduced abilities to exhibit optomotor or optokinetic responses relative to controls, with associated reductions in retinal development. Furthermore, genes associated with eye development and phototransduction were downregulated, with subsequent decreases in the immunofluorescence of neurological connections within the retina and a choroid-specific increase in apoptotic activity. We related oil-induced transcriptomic-level effects to morphological, physiological, and behavioral-level impairments in larval teleost fishes.

No description available.